CN109399588B - g-C constructed on substrate3N4Continuous film and preparation method - Google Patents

g-C constructed on substrate3N4Continuous film and preparation method Download PDF

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CN109399588B
CN109399588B CN201811559878.3A CN201811559878A CN109399588B CN 109399588 B CN109399588 B CN 109399588B CN 201811559878 A CN201811559878 A CN 201811559878A CN 109399588 B CN109399588 B CN 109399588B
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substrate
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supporting
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CN109399588A (en
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黄柏标
李慧亮
王泽岩
张晓阳
秦晓燕
郑昭科
王朋
刘媛媛
张倩倩
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605—Binary compounds of nitrogen with carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds
    • C01B13/0207—Water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention belongs to the technical field of energy, and particularly relates to a method for preparing a composite materialg-C constructed on substrate3N4A continuous film and a preparation method. Aiming at the technical problem that the prior art can not effectively prepare continuous film materials in one step without other carriers, the application provides the g-C with self-supporting property3N4The continuous film and the preparation method thereof comprise the following steps: placing the raw material powder in the upper tuyere of a furnace tube, placing the substrate in the lower tuyere of the furnace tube, and introducing Ar/CCl4Heating the gas for a period of time to obtain g-C on the substrate3N4A continuous film. The preparation method can adjust the thickness of the generated film by adjusting the gas flow and the dosage of the raw materials according to the application purpose, has simple preparation process, and has important significance in production.

Description

g-C constructed on substrate3N4Continuous film and preparation method
Technical Field
The invention belongs to the technical field of energy, and particularly relates to g-C constructed on a substrate3N4Continuous film and preparation of g-C by substrate3N4A continuous film process.
Background
The utilization of solar energy is expected to solve the energy and environmental problems faced by human beings at present, and has a series of advantages of abundant reserves, low price, environmental protection and the like, and is more and more concerned by various social circles. In recent years, as a new technology for effectively utilizing solar energy resources and converting the solar energy resources into chemical energy, a photocatalytic technology can decompose water into hydrogen and oxygen to solve problems related to energy and environment. However, the photocatalytic technology is currently faced with the problems of low photocatalytic efficiency, poor stability of part of the photocatalyst, difficult catalyst recovery and the like. Therefore, improving the catalyst preparation method, improving the catalyst efficiency and the recyclability become necessary requirements for further popularization of the application of the photocatalyst.
g-C3N4As a metal-free photocatalyst, the photocatalyst has the advantages of appropriate forbidden band position, effective visible light absorption efficiency, high stability, no toxicity, easy preparation and the like, and has attracted much attention in recent years. But powder g-C3N4The problem of catalyst recovery is a major factor limiting its application. Explore a new preparation method, fix the powder on a certain substrate, or prepare a self-supporting film material to replace the powder material to improve g-C3N4Catalyst recovery efficiency and reuse rate is an effective approach.
Li Ming et al prepared lamellar graphite phase carbon nitride nanomaterial from urea by tubular furnace high temperature heating, and the material obtained by tubular furnace heating is still a powdery material, and then binder is added to give a certain shape to the powder, so that the powder can be used as an electrode. The addition of the binder not only increases the process steps, but also affects the performance of the electrode material. In the patent publication CN106206773A, a method for preparing a graphite-type carbon nitride thin film modified electrode is provided, in a protective atmosphere, a carbon nitride raw material is heated and gasified, and then attached to a conductive substrate material, so as to obtain a graphite-phase carbon nitride thin film modified electrode. The electrode obtained by the preparation method has the advantages that the graphite phase carbon nitride film is firmly combined with the conductive substrate and can be used as the electrode, but the carbon nitride attached to the surface of the electrode is granular, is substantially powder and has no self-supporting performance.
In summary, the prior art cannot effectively prepare a continuous film material in one step without other carriers, and the development of an effective preparation method for preparing a self-supporting film is a scientific and engineering problem to be solved urgently.
Disclosure of Invention
In order to solve the technical problem, the application provides a g-C with self-supporting property3N4A continuous film and a preparation method. In this application, a tube furnace is used to prepare g-C3N4The self-supporting film is prepared by placing raw materials and substrates at two ends of a furnace tube, and placing the raw materials in CCl4Heating in gas atmosphere, and obtaining g-C on the substrate after the reaction is finished3N4A continuous film. g-C prepared in the present application3N4The continuous film can be easily peeled off from the substrate without the aid of other carriers, and is a continuous film material whose thickness can be adjusted depending on the purpose of use.
In order to achieve the technical effects, the technical scheme of the application is as follows:
in a first aspect of the invention, there is provided a self-supporting g-C3N4The preparation method of the film comprises the following steps: placing urea or melamine or dicyandiamide powder in the upper air inlet of a furnace tube, placing a substrate at the lower air inlet of the furnace tube, placing the furnace tube in a tube furnace, and introducing inert gas/CCl4Reacting the mixed gas for a period of time at a certain temperature to obtain the self-supporting film on the substrate.
In the prior art, urea, melamine or dicyandiamide powder is usually placed in a crucible for direct heating, in the application, the powder is placed in a heat-resistant container such as a porcelain boat, the porcelain boat and a substrate are placed in a furnace tube, and the g-C generated is facilitated3N4The substance is concentrated on the substrate, and the thickness of the thin film can be adjusted by adjusting the parameters of gas flow rate, raw material dose, reaction temperature and time, etc.
Preferably, the furnace tube is a quartz tube or a corundum tube, and the length of the tube is 100 cm. The quartz tube or the corundum tube can resist the temperature condition of the reaction, and other impurity ions cannot be introduced in the preparation process to influence the calcination result.
Preferably, the substrate is a single crystal substrate, a glass-based substrate, or a metal substrate.
Further preferably, the aboveThe single crystal substrate is a single crystal substrate containing an alkali metal such as lithium or sodium or an alkaline earth metal, and further LiTaO3Or LiNbO3Or a single crystal substrate such as NaCl.
Further preferably, the glass-based substrate has a glass surface carrying a thin film, and may be a glass slide, an ITO substrate, or an FTO substrate, and the glass surface is placed so as to face upward when heated.
More preferably, the metal substrate is made of a metal material that is solid at room temperature and in the reaction temperature range, and includes substrates made of materials such as Fe, Co, Ni, Ag, Au, Ta, and Nb.
Through research of the application, CCl is added into gas atmosphere4，CCl4Capable of reacting with the substrate to displace cations in the range g-C3N4The growth of the crystal nucleus provides nucleation sites which facilitate calcination to form a continuous phase film, and the formed film is easily separated from the substrate and can be easily removed from the substrate.
Preferably, the inert gas/CCl is4The mixed gas is Ar/CCl4(ii) a Further preferably, the Ar/CCl4The flow rate of (2) is 50-1000 sccm.
In the mixed gas, Ar is used as a carrier and a protective gas, the gas in the flow rate range can fully react with the raw materials to the maximum extent, and g-C to be generated is ensured at a certain gas flow speed3N4To the substrate surface, reducing adhesion on the tube wall.
Preferably, the above-mentioned reaction raw material is melamine, and the amount is 2 to 10 g.
The melamine in the dosage range can fully react in the furnace tube, the gasified melamine reaches the substrate and is condensed into a continuous film, the melamine is difficult to condense into the continuous film on the substrate when the dosage is too small, and the melamine has more residues when the dosage is too large, thereby causing waste.
Preferably, the reaction temperature is 450-700 ℃, and the reaction time is 1-10 h.
The above reaction temperature range is favorable for the generation of g-C3N4Gasification and nucleation growth, and the formation of good continuous thin film is difficult at too low or too high temperatureAnd (3) a membrane.
In a second aspect of the present invention, there is provided g-C obtained by the above-mentioned production process3N4A film.
In a third aspect of the present invention, there is provided g-C obtained by the above-mentioned production process3N4Use of a membrane as a catalyst.
The invention has the advantages of
1. The present application provides a g-C separable from a substrate3N4The preparation method of the continuous film is simple and can be completed only by one-step reaction. The prepared film can be easily peeled from the substrate and directly used as a catalyst product without adhesives or other carriers, and the thickness can be adjusted according to the use purpose.
2. In the research process of the application, CCl is added in the protective period4A gas capable of reacting with the substrate to displace cations in the range of g-C3N4The crystal nucleus growth provides sites, which is beneficial to preparing a continuous and strippable film.
3. Compared with the prior art that raw material powder is placed in a crucible and directly placed in a tube furnace for heating, the method places the powder and the substrate in the tube furnace, places the powder in an upper air port and places the substrate in a lower air port, and is beneficial to the generation of g-C3N4The method is focused on the surface of the substrate to form the film, and the thickness of the film can be conveniently adjusted by adjusting reaction parameters such as gas flow, raw material dosage and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 shows g-C prepared in the first embodiment of the present invention3N4Optical photographs of the self-supporting film on FTO glass wool substrates;
FIG. 2 shows g-C prepared in the first embodiment of the present invention3N4SEM front side pictures of the free standing film;
FIG. 3 is the present inventiong-C prepared in Ming example one3N4SEM side pictures of the free standing film;
FIG. 4 shows g-C prepared in the first embodiment of the present invention3N4An infrared spectrum of the free standing film;
FIG. 5 shows g-C prepared according to an embodiment of the present invention3N4Photocatalytic water splitting performance of self-supporting film and common powder g-C3N4Decomposing the water property comparison graph;
FIG. 6 shows g-C prepared in example seven of the present invention3N4Optical photograph of continuous film on NaCl substrate;
FIG. 7 shows g-C prepared in example seven of the present invention3N4An infrared spectrum of the continuous film;
FIG. 8 shows g-C prepared in example seven of the present invention3N4TEM images of the continuous film;
FIG. 9 shows g-C prepared according to thirteen embodiments of the present invention3N4Optical photograph of continuous film on metal Ag sheet;
FIG. 10 shows g-C prepared according to thirteen embodiments of the present invention3N4An infrared spectrum of the continuous film;
FIG. 11 is g-C prepared according to thirteen embodiments of the present invention3N4Front-side scan of continuous film;
FIG. 12 is g-C prepared according to thirteen embodiments of the present invention3N4Side-scan view of continuous film.
Fig. 13 is a photo-micrograph of an FTO substrate in comparative example one of the present invention.
FIG. 14 is a photograph of an optical photograph of a quartz substrate in a comparative example of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background of the invention, the prior art has not been able to efficiently produce a continuous, self-supporting film material in one step that can be supported without the aid of other supports, and the present application provides a g-C film material having self-supporting properties3N4A continuous film and a preparation method.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific examples and comparative examples.
Example 1
Construction of g-C on glass-based substrate3N4The preparation method of the continuous film comprises the following steps:
1) 5g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) An FTO substrate (glass side up) was placed under the melamine draw.
3) Placing the quartz tube into a tube furnace, heating for 4h at the atmosphere of 100sccm Ar/CCl4 at 550 ℃, and obtaining the self-supported g-C on the FTO glass surface3N4A film.
FIG. 1 is g-C of preparation3N4Photo-optical images of the self-supporting film, it can be seen that the film has self-supporting properties.
FIG. 2 is g-C of preparation3N4The SEM front picture of the self-supporting film shows that the prepared film has continuous two-dimensional characteristics and is formed by non-particle accumulation.
FIG. 3 shows g-C prepared in the first embodiment of the present invention3N4The SEM picture of the side surface of the self-supporting film shows that the thickness of the prepared film is 1.2um。
FIG. 4 shows g-C prepared in the first embodiment of the present invention3N4Infrared pattern of self-supporting film, and powder g-C3N4The comparison shows that the prepared self-supporting film has the same infrared spectrogram, and the chemical structure of the prepared material is verified to be g-C3N4。
FIG. 5 shows g-C prepared according to an embodiment of the present invention3N4Photocatalytic water splitting performance of self-supporting film and common powder g-C3N4Comparative water decomposition performance. With powder g-C3N4The comparison shows that the film has higher water decomposition efficiency, which indicates that the film prepared by the method can be used as an effective water decomposition photocatalyst.
Example 2
Construction of g-C on glass-based substrate3N4The preparation method of the continuous film comprises the following steps:
1) 5g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) A slide substrate (glass side up) was placed under the melamine draw.
3) Placing the quartz tube into a tube furnace, heating for 4h at the atmosphere of 100sccm Ar/CCl4 at 550 ℃, and obtaining the self-supported g-C on the FTO glass surface3N4A film.
Example 3
Construction of g-C on glass-based substrate3N4The preparation method of the continuous film comprises the following steps:
1) 2g of dicyandiamide powder is put into a porcelain boat, and then the porcelain boat is put into an air inlet of a quartz tube.
2) A slide substrate (glass side up) was placed under the melamine draw.
3) Placing the quartz tube into a tube furnace, heating for 4h at the atmosphere of 200sccm Ar/CCl4 at 550 ℃, and obtaining the self-supported g-C on the FTO glass surface3N4A film.
Example 4
One kind is atConstruction of g-C on glass-based substrates3N4The preparation method of the continuous film comprises the following steps:
1) 4g of melamine powder is put into a porcelain boat, and then the porcelain boat is put into an air inlet of a quartz tube.
2) A slide substrate (glass side up) was placed under the melamine draw.
3) Putting the quartz tube into a tube furnace, heating for 4h under the atmosphere of 300sccm Ar/CCl4 at 500 ℃, and obtaining the self-supported g-C on the FTO glass surface3N4A film.
Example 5
Construction of g-C on glass-based substrate3N4The preparation method of the continuous film comprises the following steps:
1) 2g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) An ITO substrate (glass side up) was placed under the melamine draw-off port.
3) Placing the quartz tube into a tube furnace, heating for 2h under 200sccm Ar/CCl4 atmosphere at 600 ℃, and obtaining self-supported g-C on the FTO glass surface3N4A film.
Example 6
Construction of g-C on glass-based substrate3N4The preparation method of the continuous film comprises the following steps:
1) 7g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) A slide substrate (glass side up) was placed under the melamine draw.
3) Putting the quartz tube into a tube furnace, heating for 6h under the atmosphere of 400sccm Ar/CCl4 at 550 ℃, and obtaining the self-supported g-C on the FTO glass surface3N4A film.
Example 7
Construction of g-C on single crystal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 5g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) And a piece of NaCl single crystal substrate is placed at the air outlet of the melamine lower air inlet.
3) The quartz tube was placed in a tube furnace and then heated at 100sccm Ar/CCl4Heating at 550 deg.C for 4h to obtain g-C on NaCl single crystal substrate3N4A continuous film.
FIG. 6 is g-C of preparation3N4A photo-optical image of a continuous film, from which it can be seen that the film has continuous, self-supporting properties.
FIG. 7 is g-C prepared in an example of the present invention3N4The infrared pattern of the self-supporting film shows that the prepared film has strong infrared absorption peak and standard g-C3N4The infrared spectra were consistent.
FIG. 8 is g-C prepared in an example of the present invention3N4TEM pictures of the self-supporting film show that the prepared film has continuity.
Example 8
Construction of g-C on single crystal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 5g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) A LiTaO piece is placed at the air outlet of the melamine lower air port3A single crystal substrate.
3) The quartz tube was placed in a tube furnace and then heated at 100sccm Ar/CCl4Heating at 550 deg.C for 4h in LiTaO3g-C can be obtained on a single crystal substrate3N4A film.
Example 9
Construction of g-C on single crystal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 2g of dicyandiamide powder is put into a porcelain boat, and then the porcelain boat is put into an air inlet of a quartz tube.
2) A LiTaO piece is placed at the air outlet of the melamine lower air port3A single crystal substrate.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 200sccm4Heating at 550 deg.C for 4h in LiTaO3Obtaining a single crystal substrate with a continuous g-C3N4A film.
Example 10
Construction of g-C on single crystal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 4g of melamine powder is put into a porcelain boat, and then the porcelain boat is put into an air inlet of a quartz tube.
2) A LiTaO piece is placed at the air outlet of the melamine lower air port3A single crystal substrate.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 300sccm4Heating at 500 deg.C for 4h in LiTaO3Continuous g-C on a single crystal substrate3N4A film.
Example 11
Construction of g-C on single crystal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 2g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) And a piece of NaCl single crystal substrate is placed at the air outlet of the melamine lower air inlet.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 200sccm4Heating at 600 deg.C for 2h to obtain continuous g-C on NaCl single crystal substrate3N4A film.
Example 12
Construction of g-C on single crystal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 7g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) And a piece of NaCl single crystal substrate is placed at the air outlet of the melamine lower air inlet.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 400sccm4Heating at 550 deg.C for 6h to obtain continuous g-C on NaCl single crystal substrate3N4A film.
Example 13
Construction of g-C on metal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 5g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) And placing an Ag substrate at the air outlet of the melamine lower air port.
3) The quartz tube was placed in a tube furnace and then heated at 100sccm Ar/CCl4Heating at 550 deg.C for 4h to obtain g-C on Ag sheet substrate3N4A continuous film.
FIG. 9 is g-C of preparation3N4Photo-optical images of the continuous film, it can be seen that the film is continuous and uniform.
FIG. 10 is g-C prepared in an example of the present invention3N4Infrared pattern of film, from which it can be seen that the film produced has a strong infrared absorption peak, in comparison with the standard g-C3N4The infrared spectra were consistent.
FIG. 11 is g-C prepared in an example of the present invention3N4From the SEM picture of the front side of the film, it can be seen that the prepared film has a continuous, non-particulate composition.
FIG. 12 is g-C prepared in an example of the present invention3N4From the side SEM pictures of the films, it can be seen that the thickness of the films produced is about 3 um.
Example 14
Construction of g-C on metal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 5g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) And a piece of Fe sheet substrate is placed at the air outlet of the melamine lower air port.
3) The quartz tube was placed in a tube furnace and then heated at 100sccm Ar/CCl4Heating for 4h at 550 ℃ in atmosphere to obtain g-C on the Fe sheet substrate3N4A film.
Example 15
Construction of g-C on metal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 2g of dicyandiamide powder is put into a porcelain boat, and then the porcelain boat is put into an air inlet of a quartz tube.
2) And a Co sheet substrate is placed at the outlet of the melamine lower air inlet.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 200sccm4Heating at 550 deg.C for 4h to obtain continuous g-C on Co sheet substrate3N4A film.
Example 16
Construction of g-C on metal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 4g of melamine powder is put into a porcelain boat, and then the porcelain boat is put into an air inlet of a quartz tube.
2) And a piece of Ni sheet substrate is placed at the outlet of the melamine lower air inlet.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 300sccm4Heating at 500 deg.C for 4h to obtain continuous g-C on Ni sheet substrate3N4A film.
Example 17
Construction of g-C on metal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 2g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) And placing a Nb piece substrate at the outlet of the melamine lower tuyere.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 200sccm4Heating at 600 deg.C for 2h to obtain continuous g-C on NB sheet substrate3N4A film.
Example 18
Construction of g-C on metal substrate3N4The preparation method of the continuous film comprises the following steps:
1) 7g of melamine powder was put into a porcelain boat, and then the porcelain boat was put into an upper tuyere of a quartz tube.
2) And placing a Ta sheet substrate at the outlet of the melamine lower air inlet.
3) The quartz tube was placed in a tube furnace and then Ar/CCl at 400sccm4Heating at 550 deg.C for 6h to obtain continuous g-C on Ta sheet substrate3N4A film.
Comparative example 1
The preparation was as in example 1, except that CCl was not introduced in step (3)4And introducing Ar gas carrier gas only.
As can be seen in FIG. 13, there are no g-C's on the FTO substrate3N4Film formation due to absence of CCl4The metal cations cannot be extracted as nucleation sites for g-C3N4And (5) growing the film.
Comparative example 2
The manufacturing process was the same as example 1 except that the FTO substrate was replaced with a quartz glass substrate in step (2). As can be seen from FIG. 14, after the reaction was completed, no thin film was formed on the quartz glass because metal cations in the quartz substrate could not be extracted as nucleation sites for g-C3N4And (5) growing the film.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. Self-supporting g-C3N4The preparation method of the film is characterized by comprising the following steps:
placing urea or melamine or dicyandiamide powder in the upper air inlet of a furnace tube, placing a substrate at the lower air inlet of the furnace tube, placing the furnace tube in a tube furnace, and introducing inert gas/CCl4Reacting the mixed gas at 450-700 deg.C for 1-10h to obtain free radical on the substrateSupporting the film;
the substrate is a single crystal substrate or a glass-based substrate or a metal substrate;
the single crystal substrate is a single crystal substrate containing lithium, sodium alkali metal or alkaline earth metal.
2. The self-supporting g-C of claim 13N4The preparation method of the film is characterized in that the furnace tube is a quartz tube or a corundum tube.
3. The self-supporting g-C of claim 13N4The preparation method of the film is characterized in that the single crystal substrate is LiTaO3Or LiNbO3Or a NaCl single crystal substrate.
4. The self-supporting g-C of claim 13N4The preparation method of the film is characterized in that the glass-based substrate bears the film by the glass surface.
5. The self-supporting g-C of claim 13N4The preparation method of the film is characterized in that the glass-based substrate is a glass slide, an ITO substrate or an FTO substrate.
6. The self-supporting g-C of claim 13N4The preparation method of the film is characterized in that the metal substrate is made of a metal material which is solid at normal temperature and within the reaction temperature range.
7. The self-supporting g-C of claim 13N4Method for producing a film, characterized in that the inert gas/CCl4The mixed gas is Ar/CCl4。
8. The self-supporting g-C of claim 73N4A method for producing a thin film, characterized in that the Ar/CCl4The flow rate of (2) is 50-1000 sccm.
9. g-C obtained by the preparation method of claims 1-83N4A film.
10. g-C as claimed in claim 93N4Use of a membrane as a catalyst.
CN201811559878.3A 2018-12-20 2018-12-20 g-C constructed on substrate3N4Continuous film and preparation method Active CN109399588B (en)

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